CN1400994A - Polyester tackifier and adhesive composition - Google Patents
Polyester tackifier and adhesive composition Download PDFInfo
- Publication number
- CN1400994A CN1400994A CN01805002.6A CN01805002A CN1400994A CN 1400994 A CN1400994 A CN 1400994A CN 01805002 A CN01805002 A CN 01805002A CN 1400994 A CN1400994 A CN 1400994A
- Authority
- CN
- China
- Prior art keywords
- tackifier
- polyester
- mole
- acid
- polyester tackifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a novel polyester tackifier, adhesive compositions comprising the tackifier and methods of preparation. More specifically, the polyester tackifier is obtainable by polymerising a mixture comprising a diacid or derivative thereof, a diol, and at least 6 molar % of an organic monofunctional compound, wherein the mixture is essentially free from compounds comprising 2007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:052007-8-16 11:05more than two carboxylic acid groups or alcohol groups.
Description
The present invention relates to new polyester tackifier, comprise the binder composition and the preparation method of tackifier.More particularly, polyester tackifier is to be made through polymerization by the mixture that comprises diacid or derivatives thereof, the organic monofunctional compound of two pure and mild at least 6 (mole) %, and wherein this mixture is gone up substantially and do not contained the compound with two above hydroxy-acid groups or alcohol groups.
Background of invention
In the Application Areas of many tackiness agents, synthetic polymer such as acrylic polymers have replaced material such as gelatin, starch and the vegetable jelly of natural existence to a great extent.The key of this replacement is to comprise the exploitation and the use of tackifier resins in the prescription of synthetic polymer, and this is because tackifier resins can make adhesive composition be easy to wetting substrate surface, thereby can form firm bonding.If there are not tackifier in the adhesive formula, then the viscosity of synthetic polymer and bonding stripping performance are all lower.
The tackifier of synthetic polymkeric substance have been proposed to do with various resin materials.The example of the material that proposes comprises rosin, disproportionation rosin, rosin ester (as rosiny glyceryl ester and rosiny pentaerythritol ester), the aliphatic hydrocarbon resin by oil system, aromatic hydrocarbons petroleum resin, DCPD resin, terpine resin, terpenes/phenol resins and coumarone/indene resin.
Tackifier are the resinoids that can think can be used as the stock polymer high viscosity solvent.Therefore, except our clear and definite those rise product the material of viscosifying action, this term of tackifier can not be used for any material.
Acrylic polymer compositions is as binder composition, and is existing for a long time especially for pressure sensitive adhesive (PSA) composition.Common PSA composition comprises high-molecular-weight propylene acidic group polymkeric substance and tackifying resin, also comprises softening agent, stablizer, antioxidant, filler, tinting material etc. if desired.The PSA composition should have high initial tack of adhesive, just can reach bonding mutually thereby only need contact and pressurize with adhesive surface.When bonding development, should need hardly tackiness agent and long time of matrix location.
Concerning the development adhesive formula, owing to can not make every kind of performance all reach best usually, and concerning concrete application, it is again essential reaching best performance balance, therefore, people seek the prescription that the performance that makes several tackiness agents reaches best of breed.For example, for the PSA composition that is used for label industry, people attempt to obtain the loops bond strength and stripping strength reaches optimization, simultaneously the tackiness agent that can not move in each component of lay up period.
Now, main rosin derivative (as disproportionation rosin acid) and hydrocarbon resin are at industrial tackifier as the binder composition that comprises acrylic polymers.Because rosin derivative and acrylic resin have consistency preferably, thereby are preferred.
Originally, the most important thing is the solvent-type acrylic resinoid, but caused containing the dramatic increase of the aqueous adhesive composition of acrylic polymers with the requirement of environment, health and industrial safety.Along with continuous growth, usually need improve the performance of system by tackifier resins, and development is applicable to the new tackifying resin of these systems to the demand of water-based system.
United States Patent (USP) 5120781 discloses the tackifier that are used for hot-melt adhesive composition.These tackifier are reacted under the condition that can finish esterification basically by rosin and polyvalent alcohol to be made.Make the reaction of gained reaction product and aromatic diacid then, can obtain the tackifier that rosin content is higher than 78 (weight) %.
United States Patent (USP) 4981939 relates to the tackiness agent that is used for preparing the toning agent that developing electrostatic image that the sub-print process of power supply forms uses.This toning agent comprises as principal constituent, the polyester of being made up of polyprotonic acid component and polyol component and through polyalcohol modified rosin.Polyalcohol modified rosin is to form polyester network (crosslinked) by polyvalent alcohol that contains three or three above oh groups and rosin reaction to form.
WO9942508 relates to low viscosity aromatic polyester type polyvalent alcohol, and this aromatic polyester polyvalent alcohol is made greater than 2 multi-functional polyol and chain alkyl acid, ester or oily the reaction by O-phthalic acidic group material and glycol ether, average functionality.The aromatic polyester polyvalent alcohol of making is a branched polyester.
United States Patent (USP) 3438918 relates to the rubber combination that is made by polyvalent alcohol, polyprotonic acid and oil reaction.
Therefore, an advantage of the invention is the tackifier that provide compatible with the thermotropic pressure sensitive binder composition with aqueous pressure-sensitive adhesive composition.
Another advantage of the present invention is to have improved the integrated bond performance of binder composition, has especially improved loops bond strength and stripping strength, and the tackiness agent that can not move in each component of lay up period (composition) is provided simultaneously.
Another advantage of the present invention provides and contains the rosiny polyester tackifier that minute quantity is derived from natural origin, thereby has reduced manufacturing cost, and promptly two ends are with the end capped polyester of monofunctional compound (polyester that contains no more than two rosin residues).
The present invention also has an advantage to provide the straight chain vibrin that is solid-state or liquid.
Other advantage of the present invention is illustrated by following specification sheets.
Summary of the invention
The present invention relates to polyester tackifier and the contact adhesive composition that comprises according to the polyester tackifier of claim.More particularly, the present invention relates to the polyester tackifier that obtains through polymerization by the mixture that comprises diacid or derivatives thereof, the organic monofunctional compound of two pure and mild at least 6 (mole) %, and the contact adhesive composition that comprises described polyester tackifier, wherein this mixture is gone up substantially and is not comprised the compound with two above hydroxy-acid groups or alcohol groups.The invention still further relates to the application of polyester tackifier, aqueous pressure-sensitive adhesive composition, thermotropic pressure sensitive binder composition and the method for making polyester tackifier.
Polyester tackifier can be by making at least a diacid or derivatives thereof, the organic monofunctional compound of at least a two pure and mild at least 6 (mole) % is carried out esterification and is made, wherein this mixture is gone up substantially and is not contained the compound with two above hydroxy-acid groups or alcohol groups, promptly is substantially free of to have to make compound participate in the compound of the functional group of polymerization esterification reaction more than two.Two pure and mild diacid preferably can produce alternately linear/non-branching polycondensate, and the two ends of this polycondensate are end capped with organic monofunctional compound, and organic monofunctional compound plays chain terminator, i.e. the effect of end-capping reagent.
Can be used for diacid of the present invention is organic diacid (as organic dicarboxylic acid) or derivatives thereof.So-called organic dicarboxylic acid derivative is meant that acid anhydrides or other can form any acid of ester moiety in polyester.The dicarboxylic acid that is suitable for is aliphatic, alicyclic or aromatic dicarboxylic acid, and the aromatic dicarboxylic acid or derivatives thereof is preferred.Aromatic dicarboxylic acid such as terephthalic acid and phthalic acid that the dicarboxylic acid part is more preferably arranged on contraposition or ortho position respectively.The aromatic dicarboxylic acid such as the phthalic acid that have two acid moieties on the ortho position are particularly advantageous.Aliphatic diacid can be have 4 to 12 carbon atoms, be branching or linear diacid.The term diacid also comprises the acyl chlorides and the ester of acid anhydrides and acid.The example of the diacid that is suitable for is selected from terephthalic acid, m-phthalic acid, phthalic acid, propanedioic acid, dimethyl malonic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylated pentanedioic acid, nonane diacid, sebacic acid, fumaric acid, toxilic acid, methylene-succinic acid, pimelic acid, 1,3-pentamethylene dicarboxylic acid, 1, the 2-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 2,5-norbornane dicarboxylic acid, 1, the 4-naphthalic acid, diphenic acid, 4,4 '-oxydiphenyl formic acid, diglycollic acid, 2,5-naphthalene dicarboxylic acids and/or their mixture.
Be used for aliphatic diol, alicyclic diol, aromatic diol, aklylene glycol that glycol of the present invention is preferably linear or branching, or polyalkylene glycol or their mixture, and aklylene glycol or polyalkylene glycol or their mixture are particularly preferred.Concrete polyalkylene glycol can be to have 1-4 alkylene oxide repeating unit, the more preferably polyoxyethylene glycol of 2-3 repeating unit and polypropylene glycol.Polyether polyols can comprise oxyethane and propylene oxide units.The glycol that is suitable for is selected from ethylene glycol, propylene glycol, glycol ether, triglycol, Tetraglycol 99 and dipropylene glycol or their mixture.Other glycol that is suitable for can be selected from 1, ammediol, 1,3 butylene glycol, 1, the 4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1, the 9-nonanediol, decamethylene-glycol, 2-methyl isophthalic acid, ammediol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1, ammediol, the 3-methyl isophthalic acid, 5-pentanediol, 2,2,4-trimethylammonium-1, the 6-hexylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, 2,2,4, the 4-methyl isophthalic acid, 3-cyclobutanediol, 4,4 '-methylene radical bis-phenol, 4,4 '-(2-norbornadiene)-bis-phenol, 4,4 '-dihydroxybiphenyl phenol, neighbour, between, right-dihydroxy-benzene, 4,4 '-isopropylidene bis-phenol, 2,5-naphthylidene glycol, right-Xylene glycol, pentamethylene-1,2-glycol, hexanaphthene-1, the 2-glycol, hexanaphthene-1,4-glycol, etherificate bis-phenol such as dihydroxyphenyl propane-alkylene oxide affixture and/or their mixture.
Being used for organic monofunctional compound of the present invention is monocarboxylic acid or the monohydroxy-alcohol that is suitable for.Preferred organic monofunctional compound is a monocarboxylic acid, for example is derived from the rosin of natural resource, as gum resin, and wood rosin tallol rosin.These natural rosins are mixture and/or the isomer that contain the monocarboxylic acid three ring sylvic acids of 20 carbon atoms usually.Main difference between each three ring sylvic acid is the position difference of two keys.In general, rosin is a kind of levopimaric acid that comprises, neoabietic acid, palustric acid, abietic acid, dehydroabietic acid, second dehydroabietic acid, tetrahydroabietic acid, dihydroabietic acid, the mixture of pimaric acid and isopimaric acid.The rosin that is derived from natural resource comprises that also through polymerization, isomerization, disproportionation and hydrogenant modified rosin be the rosin mixture.In addition, the also available aldehyde of rosin for example formaldehyde handle and rosin alcohol.Except that rosin, carboxylic acid such as naphthenic acid (naphtenic acid) and all be adoptable through the petroleum resin (aliphatic series and/or aromatics) of carboxylic acid or carbinol-functionalization.This mixture comprises at least 10 (mole) %, preferably the organic monofunctional compound of at least 15 (mole) %.
Polyester tackifier can comprise 15-45 (mole) % by making, more preferably 20-40 (mole) % and the diacid of 30-35 (mole) % (in total monomer) most preferably, 30-55 (mole) %, more preferably 40-55 (mole) %, and two pure and mild 6-40 (mole) % of 45-50 (mole) % (in total monomer) most preferably, more preferably 10-40 (mole) %, and most preferably the mixture of the monofunctional compound of 15-35 (mole) % (in total monomer) carries out polymerization and makes, and wherein this mixture does not contain the compound with two above hydroxy-acid groups or alcohol groups substantially.Exactly, this mixture does not contain any compound with the functionality that can participate in polyreaction more than two substantially, promptly may be present in compound or derivatives thereof in the polyester tackifier, that have two above functionality.What is called does not contain substantially to typically refer to comprise in the mixture and is lower than 5 (mole) %, preferably is lower than 1 (mole) %, most preferably is lower than the compound with two above hydroxy-acid groups or alcohol groups of 0.1 (mole) % (in total monomer).So this polyester tackifier is non-branched polyester.When glycol amount in the monomer mixture surpasses the diacid amount, adopt usually monocarboxylic acid as chain terminator with " sealing " polyester, thereby obtain with the end capped polyester of monocarboxylic acid (rosin).The diacid amount surpasses in the situation of glycol amount in monomer mixture, adopt monohydroxy-alcohol as chain terminator with the sealing polyester.
Polyester tackifier of the present invention makes through polycondensation (esterification) under inert atmosphere.In addition, polycondensation also can be carried out in the presence of the esterifying catalyst of at least a catalytic amount.Usually, esterifying catalyst comprises phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, tosic acid, Quilonum Retard, calcium hydroxide, zinc oxide or their mixture.In addition, if adopt one or more rosin, then also can there be the disproportionation catalyzer.The example of disproportionation catalyzer can be through load or unsupported metal such as palladium, nickel and platinum and iodine, iodide, sulfide, monobasic and polyphenol thioether (being starch phenol (amylophenol) disulfide polymer).The consumption of esterifying catalyst is generally about 0.01-0.1 (weight) %, particularly 0.05-0.07 (weight) %, and the disproportionation catalyst consumption is generally about 0.1-0.3% (all wt per-cent is all in total monomer weight).Adopt in the embodiment of esterification and/or disproportionation catalyzer at those, catalyzer adds after being preferably in structural unit fusion again.
Monomer mixture through being everlasting 220 ℃-280 ℃, most preferably carries out polyreaction at 250 ℃-260 ℃, usually at 150 ℃-350 ℃ till the distillation of water stops.In general, the reaction times can change in 10 hours to 30 hours, more preferably at 12 hours-20 hours, and most preferably was 14 hours-16 hours.Usually, be lower than 25 milligrams of KOH/ gram and/or acid number and change and reduced to 1 milligram below KOH/g/ hour the time, can make reaction terminating when acid number drops to.
The preferred number-average molecular weight of vibrin according to the present invention (Mn) is 400-6000,400-2000 more preferably, and most preferably be 500-1800.The molecular weight distribution of resin is measured with heterogeneity index, is generally 1.1-2.0, more preferably 1.1-1.3.
Vibrin physical condition at room temperature can be solid-state or liquid, decides with reaction conditions and used monomer, particularly decides with the type of used glycol.New vibrin preferably with other tackifier (as the rosiny pentaerythritol ester) blend mutually.
The present invention also relates to comprise the contact adhesive composition of polymkeric substance and above-mentioned polyester tackifier.The contact adhesive composition that comprises above-mentioned polyester tackifier is particularly advantageous to the application under the low temperature, for example has good bond properties when temperature is lower than 0 ℃ of use.In addition, when all or part of conventional tackifier such as the tetramethylolmethane base tackifier novel polyester tackifier with above-mentioned definition replaces, can make quite or better binder composition of thickening property with lower cost.
The invention still further relates to the application of tackifier in contact adhesive composition.
According to a preferred embodiment of the invention, polyester tackifier is to be included in aqueous pressure-sensitive adhesive (PSA) composition that contains other polymkeric substance.
Tackifier are preferably with water dispersion form feed.Adopt the phosphate ester surfactants of dispersion agent such as ethoxylation tackifier can be dispersed in the water.Dispersant dosage is generally 2-6 (weight) % of tackifier.The polyester tackifier amount is 40-65 (weight) % in the tackifier water dispersion, more preferably 50-57 (weight) % (in the tackifier dispersion total amount).
Comprise polymkeric substance according to contact adhesive composition of the present invention and aqueous adhesive composition.The examples of polymer that is suitable for is natural rubber and synthetic rubber such as (co) polychloroprene rubber, styrene butadiene rubbers, the SIS segmented copolymer, the SBS segmented copolymer, VAE (vinyl acetate ethylene copolymers), paracril and polyisobutylene rubber, acrylic ester polymer, acrylic polymers such as acrylate and methacrylate polymers or their mixture.
The polymkeric substance that is specially adapted to according to aqueous adhesive composition of the present invention is acrylic polymers and/or the acrylate copolymer that is dispersed in aqueous phase, and this polymkeric substance or copolymer dispersion can be made through letex polymerization by various alkene and acrylate such as 2-EHA and butyl acrylate.Amount of polymers in the aqueous polymer dispersion form is 50-70 (weight) %, preferred 55-65 (weight) % (in the polymeric dispersions total amount).
Aqueous adhesive composition comprises 10-40 (weight) % usually, the tackifier dispersion of preferred 20-30 (weight) % (in the waterborne compositions total amount), and 60-90 (weight) %, the polymeric dispersions of preferred 70-80 (weight) % (in the waterborne compositions total amount).
Known other compound of person skilled in the art also can be included in the aqueous adhesive composition, softening agent for example, stablizer, antioxidant, filler, tinting material etc.
According to another preferred embodiment, the vibrin tackifier are also contained in thermotropic pressure sensitive tackiness agent (PSA) composition.Therefore, the present invention includes the thermotropic pressure sensitive binder composition that contains above-mentioned polyester tackifier.This hot-melt adhesive composition preferably comprises the fluoropolymer resin of the ethene copolymer that is formed by ethene and other various monomers such as vinyl-acetic ester, methyl acrylate, ethyl propenoate and other acrylate.In addition, styrene block copolymer (SBC) is as SBS, and styrene-isoprene-phenylethene (SIS) and styrene-ethylene-butylene-styrene (SEBS) all can be used among the present invention, and EVA and SBS base co-polymer are particularly preferred.
In addition, ethene copolymer base hot-melting type composition can comprise ceresine such as paraffin and Microcrystalline Wax and synthetic wax such as polyethylene wax and Poly Propylene Wax.Other animal wax and vegetable wax also can adopt.
The example that is used for SBS base hot-melting type composition oil of the present invention preferably includes higher mineral oil of molecular weight and olefin oligomer.Other vegetables oil and/or animal oil also can adopt.
Can preferably add 10-60 (weight) %, the more preferably polyester tackifier of 30-60 (weight) % (in total composition) to the hot-melting type composition.
Suitable 10-75 (weight) %, more preferably 10-40 (weight) % of adding of styrene block copolymer.
Can add 5-50 (weight) %, be preferably the wax of 5-30 (weight) %.
Binder composition is that the consumption of polymer/copolymer in waterborne compositions or the hot-melting type composition and other compound is not critical, but changeable, to obtain the preferred properties of binder composition.Other compound can according to the state of binder composition as be dispersed in water-based mutually in, liquid or solid-state and select any physical condition.
The present invention is further illustrated by following embodiment, yet these embodiment are not limitations of the present invention.All units (share or per-cent) except as otherwise noted, all by weight.
Embodiment
The product property that the listed performance of table 1 is made for the raw material that adopts this paper regulation.Being used for expression structure unit (a) and (b) in the table represents respectively with abbreviation (c): deg is a glycol ether, mpdiol is the 2-methyl isophthalic acid, ammediol, chdm is 1, the 4-cyclohexanedimethanol, meg is an ethylene glycol, adipic is a hexanodioic acid, pza is a Tetra hydro Phthalic anhydride, and aze is a nonane diacid, and rosin is natural Chinese gum rosin, napht is a naphthenic acid, HCR is carboxylic acid functionalized petroleum hydrocarbon resin (as the hydrocarbon resin AG-12-28 of modification, Neville Chemical Company makes), and Form ros is the natural Chinese gum rosin through formaldehyde treated.
The performance of the various vibrin of table 1
Ratios is respectively in the ratio of the glycol/diacid/end-capping reagent of weight % (with gross weight) expression, Mn=number-average molecular weight (gram/mole), the Mw/Mn=heterogeneity index, the viscosity that Visco=measures in the time of 50 ℃ with the Brookfield viscometer (the milli handkerchief. second), AV=acid number (milligram KOH/ gram), the SP=softening temperature (℃), the Color=Gardner color standards.
| ??No. | Glycol (a) | Diacid (b) | End-capping reagent (c) | Raw material ratio | ???Mn | ???Mw/Mn | ???Visco | ???SP | ??AV | ??Color |
| ????1 | ????Deg | ???Adipic | ??Rosin | ??34/33/33 | ??840 | ????1.2 | ??525 | ??- | ??24 | ????10 |
| ????2 | ????Deg | ???Pza | ??Napht | ??35/33/32 | ??950 | ????1.1 | ??1600 | ??- | ??13 | ????12 |
| ????3 | ????Mpdiol | ???Aze/pza | ??Rosin | ??29/31/8/32 | ??960 | ????1.1 | ??1900 | ??- | ??18 | ????6 |
| ????4 | ????Deg | ???Pza | ??Rosin | ??30/14/56 | ??560 | ????1.1 | ??5150 | ??- | ??20 | ????4.5 |
| ????5 | ????Deg | ???Pza | ??Rosin | ??34/33/33 | ??870 | ????1.1 | ??11200 | ??- | ??22 | ????2 |
| ????6 | ????Deg | ???Pza | ??Rosin | ??40/51/9 | ??1600 | ????1.3 | ??200000 | ??- | ??25 | ????3.5 |
| ????7 | ????Meg | ???Pza | ??Rosin | ??24/38/38 | ??740 | ????1.1 | ??- | ??44.7 | ??15 | ????4 |
| ????8 | ????Deg | ???Pza | ??HCR | ??26/36/38 | ??1610 | ????1.2 | ??- | ??63.5 | ??23 | ????9 |
| ????9 | ????Deg | ???Pza | ??Form ??ros | ??19/9/72 | ??680 | ????1.2 | ??- | ??76.0 | ??78 | ????14 |
| ????10 | ????chdm | ???Pza | ??Rosin | ??42/29/29 | ??910 | ????1.2 | ??- | ??79.8 | ??16 | ????3 |
Embodiment 1 and 2 has done detailed description to No.5 and 4 respectively.These embodiment have illustrated in more detail as the preparation of the vibrin of tackifier and application.
Embodiment 1
In device has the reaction vessel of nitrogen inlet tube, thermometer, agitator and rectifying column, pack into 500 gram Chinese gum rosin, 505 gram Tetra hydro Phthalic anhydrides and 530 gram glycol ethers.Heat this reaction mixture to forming uniform melt, add 2 gram Vultac2 (Elf Atochem) disproportionation catalysts then.The temperature of reaction mixture is risen to 180 ℃ and kept 1 hour, make temperature progressively rise to 250 ℃ then.Allow be reflected at and carried out under this temperature 20 hours, when the distillation of water stops, making reaction terminating.Make the acid number AV=22 milligram KOH/ gram of product, viscosity (Brookfield, 50 ℃) is 11200 milli handkerchiefs. second, number-average molecular weight Mn=870, polymolecularity Mw/Mn=1.1, Ge Shi colour code are 2.
According to the described step of WO9412272 (US5552519) 1500 these vibrin of gram are dispersed in the water, obtain tackifier dispersion (A).
With 350 gram vibrin and the stable ester gum blend of 650 grams.By 60 gram ethoxylated phosphate esters tensio-active agents blend is dispersed in the water then, obtains tackifier dispersion (B).
Embodiment 2
At device nitrogen inlet tube is arranged, thermometer, the 800 gram Chinese gum rosin of packing in the reaction vessel of agitator and rectifying column, 200 gram Tetra hydro Phthalic anhydrides and 424 gram glycol ethers.The reacting by heating mixture makes its temperature rise to 180 ℃, and keeps 1 hour.Make mixture temperature rise to 250 ℃ gradually then, allow be reflected at and carried out under this temperature 17 hours, when the distillation of water stops, making reaction terminating.The acid number AV=20 milligram KOH/ gram of the product that makes, viscosity (Brookfield, 50 ℃) they are 5150 milli handkerchiefs. second, number-average molecular weight Mn=560, polymolecularity Mw/Mn=1.1, Ge Shi colour code are 4.5.
With 700 these vibrin of gram and 300 gram rosiny pentaerythritol ester blend.By 60 gram ethoxylated phosphate esters tensio-active agents blend is dispersed in the water then, obtains tackifier dispersion (C).
The bond test result
Acronal v210, Primal EP5560 and Flexcryl1625 are respectively available from BASF, Rohm﹠amp; The water soluble acrylic acid polymer dispersion of Haas Co. and Air Products.Table 2 has been listed PSA performance (the FINAT test method of self adhesive material that adopts standard test methods to record; Shearing test: FTM8; Stripping test: FTM1; Loops bond test: FTM9).Every kind of binder composition is to be blended into the water-based form by weight, and is coated on the polysiloxane release liner material.Coating wt be 20 ± 1 the gram/square metre.Film 90 ℃ of dryings 3 minutes.Film is changeed on the level and smooth paper finishing material that is applied to 80 grams,, and under room temperature and 50% humidity, place and spend the night then coated with separate paper.
The test of table 2 bond properties
Shear=1000 gram/square inch is to the shearing of glass; LDPE tests on untreated film, and stripping test is 180 ° and peels off; The CF=cohesive failure; The soft little cohesive failure of sCF=; The AF=adhesion failure; The distortion of PD=paper; The slight paper of sPT=is torn.
| System | ???shear | Peel off | Loops is bonding | ||
| Hour | ????LDPE ????(N) | Carton paper (N) | Steel (N) | ????LDPE ????(N) | |
| ????100％Acronal?V210 | ????27.0 | ????5.1 | ????12.5 | ????12.1 | ????5.1 |
| ????CF | ????AF | ????AF | ????AF | ????AF | |
| ????70％Acronal?V210/ | ????0.6 | ????13.9 | ????19.3 | ????11.6 | ????8.9 |
| 30% tackifier dispersion A | ????AF/PD | ????AF/sCF | ????AF | ????AF | |
| ????70％Acronal?V210/ | ????6.3 | ????13.2 | ????20.1 | ????17.3 | ????10.7 |
| 30% tackifier dispersion B | ????CF | ????AF | ????AF/sPT | ????AF | ????AF |
| ????70％Acronal?V210/ | ????3.5 | ????11.1 | ????18.3 | ????14.9 | ????11.9 |
| 30% tackifier dispersion C | ????CF | ????AF/PD | ????AF/sPT | ????AF | ????AF |
| ????100％Primal?EP5560 | ????11.2 | ????2.6 | ????4.0 | ????9.1 | ????3.0 |
| ????CF | ????AF | ????AF | ????AF | ????AF | |
| ????70％Primal?EP5560 | ????1.0 | ????4.6 | ????14.3 | ????8.3 | ????4.5 |
| 30% tackifier dispersion A | ????AF | ????AF/sCF | ????AF | ????AF | |
| ????70％Primal?EP5560/ | ????4.0 | ????12.5 | ????18.9 | ????11.4 | ????9.9 |
| 30% tackifier dispersion C | ????CF | ????AF/PD | ????AF | ????AF | ????AF |
| ????100％Flexcryl?1625 | ????19.3 | ????5.3 | ????14.6 | ????9.9 | ????5.3 |
| ????AF | ????AF | ????AF | ????AF | ||
| ????70％Flexcryl?1625 | ????0.5 | ????10.3 | ????18.7 | ????9.2 | ????6.5 |
| 30% tackifier dispersion A | ????AF/PD | ????AF/sCF | ????AF | ????AF | |
| ????70％Flexcryl?1625 | ????1.3 | ????13.0 | ????20.1 | ????16.0 | ????10.6 |
| 30% tackifier dispersion B | ????AF/PD | ????AF/sCF | ????AF | ????AF | |
Can be reached a conclusion by table 2 result: the dispersion that contains new polyester tackifier has been improved stripping performance and loops bond properties.
Claims (16)
1. polyester tackifier, it is characterized in that these tackifier are to be made through polymerization by the mixture that comprises diacid or derivatives thereof, the organic monofunctional compound of two pure and mild at least 6 (mole) %, wherein this mixture does not conform to the compound with two above hydroxy-acid groups or alcohol groups on substantially.
2. according to the polyester tackifier of claim 1, it is characterized in that these tackifier are to be made through polymerization by the mixture that comprises 15-45 (mole) % diacid, the organic monofunctional compound of 30-55 (mole) % two pure and mild 6-40 (mole) %.
3. according to the polyester tackifier of claim 1, it is characterized in that mixture comprises the organic monofunctional compound of 6 (mole) %-40 (mole) %.
4. according to the polyester tackifier of claim 1, it is characterized in that mixture comprises the organic monofunctional compound of 10 (mole) %-40 (mole) %.
5. each polyester tackifier is characterized in that mixture comprises the organic monofunctional compound of 15 (mole) %-35 (mole) % in requiring according to aforesaid right.
6. each polyester tackifier is characterized in that organic monofunctional compound is monocarboxylic acid or monohydroxy-alcohol in requiring according to aforesaid right.
7. according to the polyester tackifier of claim 6, it is characterized in that organic monofunctional compound is a monocarboxylic acid.
8. according to the polyester tackifier of claim 7, it is characterized in that monocarboxylic acid is the rosin that is derived from natural origin.
9. each polyester tackifier is characterized in that tackifier are non-branched polyesters in requiring according to aforesaid right.
10. each polyester tackifier is characterized in that diacid is an aromatic diacid in requiring according to aforesaid right.
11. each polyester tackifier is characterized in that glycol is aklylene glycol or polyalkylene glycol or their mixture in requiring according to aforesaid right.
12. a contact adhesive composition, said composition comprise the polyester tackifier of polymkeric substance and claim 1-11 definition.
13. by the polyester tackifier of claim 1-11 definition purposes as the pressure sensitive composite tackifier.
14. an aqueous pressure-sensitive adhesive composition, said composition comprise the polyester tackifier of polymkeric substance and claim 1-11 definition.
15. a thermotropic pressure sensitive binder composition, said composition comprise the polyester tackifier of claim 1-11 definition.
16. make method, it is characterized in that this polyester tackifier made through polymerization by monomer under the temperature of inert atmosphere and 150 ℃-350 ℃ by the polyester tackifier of claim 1-11 definition.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18331000P | 2000-02-17 | 2000-02-17 | |
| EP00850030 | 2000-02-17 | ||
| US60/183,310 | 2000-02-17 | ||
| EP00850030.8 | 2000-02-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1400994A true CN1400994A (en) | 2003-03-05 |
| CN1223644C CN1223644C (en) | 2005-10-19 |
Family
ID=26074187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01805002.6A Expired - Fee Related CN1223644C (en) | 2000-02-17 | 2001-02-09 | Polyester tackifier and adhesive composition |
Country Status (14)
| Country | Link |
|---|---|
| US (2) | US6653398B2 (en) |
| EP (1) | EP1255795B1 (en) |
| JP (1) | JP4490023B2 (en) |
| CN (1) | CN1223644C (en) |
| AT (1) | ATE301176T1 (en) |
| AU (1) | AU780249B2 (en) |
| BR (1) | BR0108306B1 (en) |
| CA (1) | CA2400202C (en) |
| DE (1) | DE60112404T2 (en) |
| DK (1) | DK1255795T3 (en) |
| ES (1) | ES2243443T3 (en) |
| NZ (1) | NZ520252A (en) |
| PT (1) | PT1255795E (en) |
| WO (1) | WO2001060939A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108350342A (en) * | 2015-11-30 | 2018-07-31 | 哈利玛化成株式会社 | Tackifying resin and adhesion agent composition |
| CN109863200A (en) * | 2016-09-23 | 2019-06-07 | 科腾化学品有限责任公司 | Oligoester composition and its preparation and application |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0107223D0 (en) * | 2001-03-23 | 2001-05-16 | Ici Plc | Resin composition |
| US9023929B2 (en) * | 2004-02-13 | 2015-05-05 | Lawter, Inc. | Tackifier dispersion |
| US20070135542A1 (en) * | 2005-12-08 | 2007-06-14 | Boonstra Lykele J | Emulsifiers for use in water-based tackifier dispersions |
| US7579394B2 (en) * | 2007-01-16 | 2009-08-25 | Xerox Corporation | Adhesion promoter |
| US7754812B2 (en) | 2007-01-16 | 2010-07-13 | Xerox Corporation | Adhesion promoter |
| US8357763B2 (en) * | 2007-05-02 | 2013-01-22 | Xerox Corporation | Adhesion promoter |
| FR2955586B1 (en) * | 2010-01-28 | 2013-02-08 | Eurovia | SYNTHETIC BINDER ESSENTIALLY BASED ON MATERIALS RESULTING FROM RENEWABLE RESOURCES, ESPECIALLY OF VEGETABLE ORIGIN, AND ITS APPLICATIONS IN ROAD TECHNOLOGY |
| DE102010009230A1 (en) * | 2010-02-25 | 2011-08-25 | Giesecke & Devrient GmbH, 81677 | Highly flexible film composite material and its use in card bodies |
| JP5734779B2 (en) * | 2010-12-24 | 2015-06-17 | 富士フイルム株式会社 | Polyester polymer, resin composition, molded article, and film |
| WO2015048415A2 (en) | 2013-09-27 | 2015-04-02 | Arizona Chemical Company, Llc | Rosin esters and compositions thereof |
| EP3049490A2 (en) | 2013-09-27 | 2016-08-03 | Arizona Chemical Company, LLC | Rosin esters and compositions thereof |
| BR112016006762A2 (en) | 2013-09-27 | 2017-08-01 | Arizona Chemical Co Llc | compositions containing ethylene polymers |
| CN107922815B (en) | 2015-08-18 | 2021-08-06 | 3M创新有限公司 | Chemical resistant polyester pressure sensitive adhesives |
| GB2555764B (en) * | 2015-10-12 | 2022-06-15 | Lewtas Science & Tech Ltd | Improvements in or relating to energetic materials |
| KR20180103941A (en) * | 2015-12-31 | 2018-09-19 | 크라톤 케미칼, 엘엘씨 | Oligo esters and compositions thereof |
| CN112041363B (en) | 2018-03-13 | 2022-12-23 | 陶氏环球技术有限责任公司 | Viscoelastic foam |
| KR102660030B1 (en) | 2018-10-01 | 2024-04-22 | 덴카 주식회사 | adhesive sheet |
| CN113614127A (en) | 2019-03-01 | 2021-11-05 | 陶氏环球技术有限责任公司 | Adhesion promoter composition |
| EP4083104B1 (en) * | 2021-04-28 | 2023-08-16 | Lawter, Inc. | Tackifier for adhesive composition |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2560033A (en) * | 1950-09-08 | 1951-07-10 | Firestone Tire & Rubber Co | Friction element bonding film |
| US3300543A (en) * | 1957-09-23 | 1967-01-24 | Avery Products Corp | Stabilized pressure sensitive adhesive consisting of saturated polyester and vinyl chloride polymer |
| US3072519A (en) * | 1958-08-29 | 1963-01-08 | Allied Record Mfg Co | Method of making phonograph record blanks from composite material |
| US3345206A (en) * | 1963-07-22 | 1967-10-03 | Johnson & Johnson | Adhesive composition containing a carboxyl modified elastomer, adhesive sheet coatedtherewith, and method of making the adhesive sheet |
| US3438918A (en) * | 1966-12-01 | 1969-04-15 | American Cyanamid Co | Ethylene-propylene terpolymer rubber composition with improved tack |
| US4058645A (en) * | 1973-08-24 | 1977-11-15 | Mobil Oil Corporation | Heat sealable thermoplastic films |
| JPS5583435A (en) * | 1978-12-20 | 1980-06-23 | Hitachi Ltd | Resin mold stator |
| US4457718A (en) * | 1981-02-12 | 1984-07-03 | Color Communications, Inc. | Color display product |
| JPS60155225A (en) * | 1984-01-24 | 1985-08-15 | Kuraray Co Ltd | Novel polyester, adhesive comprising the same, and laminate and laminated hollow vessel prepared therefrom |
| US4876304A (en) * | 1986-05-15 | 1989-10-24 | National Distillers And Chemical Corp. | Polyvinyl chloride compositions plasticized with copolyesters |
| JPH079546B2 (en) | 1986-11-17 | 1995-02-01 | 日本合成化学工業株式会社 | Binder for toner |
| JPH05320607A (en) * | 1991-01-29 | 1993-12-03 | Nippon Shokubai Co Ltd | Production of resin for pressure-sensitive adhesive |
| US5120781A (en) * | 1991-05-07 | 1992-06-09 | Union Camp Corporation | Acid-modified polyhydric alcohol rosin ester tackifiers and hot melt adhesive compositions containing those tackifiers |
| SE9203499L (en) | 1992-11-20 | 1994-05-21 | Eka Nobel Ab | Rosin derivative as surfactant |
| US5420229A (en) * | 1993-11-16 | 1995-05-30 | Resinall Corporation | Flushing vehicles for preparing flushed organic pigments and method for preparing the same |
| KR100496494B1 (en) * | 1995-08-22 | 2005-06-22 | 코그니스 코포레이션 | Smokeless two-cycle engine lubricants |
| WO1999042508A1 (en) | 1998-02-23 | 1999-08-26 | Stepan Company | Low viscosity polyester polyols and methods for preparing same |
-
2001
- 2001-02-09 BR BRPI0108306-6A patent/BR0108306B1/en not_active IP Right Cessation
- 2001-02-09 WO PCT/SE2001/000264 patent/WO2001060939A1/en active IP Right Grant
- 2001-02-09 DK DK01904739T patent/DK1255795T3/en active
- 2001-02-09 JP JP2001560311A patent/JP4490023B2/en not_active Expired - Fee Related
- 2001-02-09 PT PT01904739T patent/PT1255795E/en unknown
- 2001-02-09 CA CA002400202A patent/CA2400202C/en not_active Expired - Fee Related
- 2001-02-09 NZ NZ520252A patent/NZ520252A/en not_active IP Right Cessation
- 2001-02-09 DE DE60112404T patent/DE60112404T2/en not_active Expired - Lifetime
- 2001-02-09 CN CN01805002.6A patent/CN1223644C/en not_active Expired - Fee Related
- 2001-02-09 AT AT01904739T patent/ATE301176T1/en active
- 2001-02-09 ES ES01904739T patent/ES2243443T3/en not_active Expired - Lifetime
- 2001-02-09 EP EP01904739A patent/EP1255795B1/en not_active Expired - Lifetime
- 2001-02-09 AU AU32564/01A patent/AU780249B2/en not_active Ceased
- 2001-02-16 US US09/785,098 patent/US6653398B2/en not_active Expired - Fee Related
-
2003
- 2003-06-06 US US10/456,429 patent/US6989413B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108350342A (en) * | 2015-11-30 | 2018-07-31 | 哈利玛化成株式会社 | Tackifying resin and adhesion agent composition |
| US10781344B2 (en) | 2015-11-30 | 2020-09-22 | Harima Chemicals, Incorporated | Tackifier resin and pressure-sensitive adhesive composition |
| CN109863200A (en) * | 2016-09-23 | 2019-06-07 | 科腾化学品有限责任公司 | Oligoester composition and its preparation and application |
| CN109863200B (en) * | 2016-09-23 | 2022-01-18 | 科腾化学品有限责任公司 | Oligoester compositions and methods of making and using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| NZ520252A (en) | 2004-03-26 |
| WO2001060939A1 (en) | 2001-08-23 |
| US6653398B2 (en) | 2003-11-25 |
| EP1255795B1 (en) | 2005-08-03 |
| DE60112404D1 (en) | 2005-09-08 |
| ES2243443T3 (en) | 2005-12-01 |
| AU780249B2 (en) | 2005-03-10 |
| BR0108306A (en) | 2003-03-05 |
| CN1223644C (en) | 2005-10-19 |
| PT1255795E (en) | 2005-10-31 |
| EP1255795A1 (en) | 2002-11-13 |
| AU3256401A (en) | 2001-08-27 |
| BR0108306B1 (en) | 2010-11-30 |
| JP4490023B2 (en) | 2010-06-23 |
| US6989413B2 (en) | 2006-01-24 |
| US20030212201A1 (en) | 2003-11-13 |
| CA2400202C (en) | 2009-10-20 |
| US20010021737A1 (en) | 2001-09-13 |
| JP2003523444A (en) | 2003-08-05 |
| CA2400202A1 (en) | 2001-08-23 |
| DE60112404T2 (en) | 2006-06-01 |
| DK1255795T3 (en) | 2005-12-12 |
| ATE301176T1 (en) | 2005-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1223644C (en) | Polyester tackifier and adhesive composition | |
| EP0865473B1 (en) | Radiation cross-linkable branched polyester compositions which are water-dispersible and processes | |
| US7452941B2 (en) | Terpene resin and hydrocarbon resin-based surfactants and aqueous dispersion of tackifier resins | |
| CN1281680C (en) | Sulfonated copolyester based water -dispersible hot melt adhesive | |
| CN101821332A (en) | End use applications prepared from certain block copolymers | |
| AU602920B2 (en) | Emulsion polymerized sec-butyl acrylate latexes suitable for use as pressure sensitive adhesives and process for preparing the same | |
| CA1047690A (en) | Copolyesters, method of manufacturing same, and hot melt adhesive compositions incorporating same | |
| CN1918202A (en) | Tackifier dispersion | |
| CN106496500A (en) | A kind of high tack hot melt polyurethane adhesive and preparation method thereof | |
| CN102549095A (en) | Radiation-cure removal type pressure-sensitive adhesive sheet | |
| JP2007051282A (en) | Reactive hot-melt adhesive | |
| EP0088510A2 (en) | Improvement in or relating to petroleum resins | |
| KR20040104552A (en) | Rubber-acrylic adhesive formulation | |
| CN1745155A (en) | Packaging tape adhesive composition and packaging tape comprising it | |
| CN111690263B (en) | Tackifier resin emulsion, water-based adhesive and/or cohesive agent composition, and adhesive and/or cohesive sheet | |
| EP2821454B1 (en) | Unsaturated photo-curable bio-based adhesive composition | |
| CN115244098A (en) | Mineral-free oil pressure sensitive adhesive | |
| CN1119203A (en) | Releasable pressure sensitive adhesive composition | |
| CN110093135A (en) | A kind of density board polyurethane adhesive suitable for ultralow temperature | |
| KR102507153B1 (en) | Hot melt adhesive composition and method for preparing the same | |
| CN104428380A (en) | Hot melt adhesive | |
| JPS6239645A (en) | Elastomer composition | |
| CN1798781A (en) | Resin composition | |
| ZANKER | 116 Resins | |
| CN1180090A (en) | Water base high molecular water-proof paint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: BORDEN CHEM INC. Free format text: FORMER OWNER: AKZO NOBEL N.V. Effective date: 20110107 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: ARNHEM, HOLLAND TO: OHIO STATE, USA |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20110107 Address after: American Ohio Patentee after: Borden Chem Inc. Address before: Holland Arnhem Patentee before: Akzo Nobel N. V. |
|
| ASS | Succession or assignment of patent right |
Owner name: LAUTH OY Free format text: FORMER OWNER: BORDEN CHEM INC. Effective date: 20120229 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20120229 Address after: Illinois Instrunment Patentee after: Raute Oyj Address before: American Ohio Patentee before: Borden Chem Inc. |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20051019 Termination date: 20140209 |